Ring Enlarging Dipolar Cycloadditions of Chlorosulfonylisocyanate to Epoxides

Lorincz, Tibor; Erden, İhsan; Näder, Reinhard; Meijere, Armin de

doi:10.1080/00397918608057699

Cited by 15 publications

(7 citation statements)

References 13 publications

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“…On the other hand, in the study of De Meijere and co-workers, the reaction started at −78 °C to give five-membered cyclic carbonates and oxazolidinones using seven examples [42]. Three of these attempts resulted in five-membered cyclic carbonates as the sole products while in two cases oxazolidinones were produced, and the other two reactions gave mixtures of two products.…”

Section: Resultsmentioning

confidence: 99%

“…These reports prompted us to explore this reaction in more detail. In our Scheme 2: Proposed mechanisms by Keshava Murthy and Dhar [41] and De Meijere and co-workers [42].…”

Section: Introductionmentioning

confidence: 93%

“…In 1984, Keshava Murthy and Dhar reported the synthesis of five-membered cyclic carbonates and oxazolidinones from various epoxides in two steps using CSI and KOH in benzene/dichloromethane [40,41]. In 1986, De Meijere and co-workers reported the cycloaddition of CSI to epoxides at −78 °C to give five-membered cyclic carbonates and oxazolidinones [42]. They reported seven examples; three of these attempts resulted in five-membered cyclic carbonates as the sole product while two cases produced oxazolidinones, and the other two reactions gave mixtures of two products.…”

Section: Introductionmentioning

confidence: 99%

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One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

Demir¹,

Sarı²,

Çetinkaya³

et al. 2020

Beilstein J. Org. Chem.

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The one-pot reaction of chlorosulfonyl isocyanate (CSI) with epoxides having phenyl, benzyl and fused cyclic alkyl groups in different solvents under mild reaction conditions without additives and catalysts was studied. Oxazolidinones and five-membered cyclic carbonates were obtained in ratios close to 1:1 in the cyclization reactions. The best yields of these compounds were obtained in dichloromethane (DCM). Together with 16 known compounds, two novel oxazolidinone derivatives and two novel cyclic carbonates were synthesized with an efficient and straightforward method. Compared to the existing methods, the synthetic approach presented here provides the following distinct advantageous: being a one-pot reaction with metal-free reagent, having shorter reaction times, good yields and a very simple purification method. Moreover, using the density functional theory (DFT) method at the M06-2X/6-31+G(d,p) level of theory the mechanism of the cycloaddition reactions has been elucidated. The further investigation of the potential energy surfaces associated with two possible channels leading to oxazolidinones and five-membered cyclic carbonates disclosed that the cycloaddition reaction proceeds via an asynchronous concerted mechanism in gas phase and in DCM.

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Section: Resultsmentioning

confidence: 99%

“…These reports prompted us to explore this reaction in more detail. In our Scheme 2: Proposed mechanisms by Keshava Murthy and Dhar [41] and De Meijere and co-workers [42].…”

Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: theoretical evidence for an asynchronous concerted pathway

Demir¹,

Sarı²,

Çetinkaya³

et al. 2020

Beilstein J. Org. Chem.

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“…As a continuation of these studies, we performed one-pot synthesis of the titled compounds by optimizing the reaction of CSI with epoxides in different solvents under mild conditions. Compared to the De Meijere and coworkers's method, the study provided higher yields using simple purification method in shorter reaction times under the mild reaction [41] and De Meijere and coworkers [42].…”

Section: Introductionmentioning

confidence: 89%

“…Meijere and coworkers reported the cyclic addition of CSI to epoxides at -78 o C to give five membered cyclic carbonates and oxazolidinones [42]. They reported seven reactions; three of these attempts resulted in five membered cyclic carbonates as the sole product while two cases produced oxazolidinones, and other two reactions gave the mixture of two products.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Synthesis of Oxazolidinones and Five-Membered Cyclic Carbonates from Epoxides and Chlorosulfonyl isocyanate: Theoretical Evidence for the Asynchronous Concerted Pathway

Demir¹,

Sarı²,

Çetinkaya³

et al. 2020

Preprint

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The one-pot reaction of chlorosulfonyl isocyanate (CSI) with epoxides having substituted phenyl, benzyl and fused cyclic alkyl groups in different solvents under mild reaction conditions without additives and catalysts was studied. Oxazolidinones and five-membered cyclic carbonates were obtained with a ratio close to (1:1) in the cyclization reactions. The best reaction conversion for the synthesis of these compounds was carried out in dichloromethane (DCM). The method presented here has distinct advantageous over the existing methods such as one-pot reaction, shorter reaction times, metal-free reagent, good yields and very simple purification method. The mechanism for the cycloaddition reactions has been elucidated using density functional theory (DFT) method at the M06-2X/6-31+G(d,p) level. The investigation of the potential energy surfaces associated with two possible channels leading to oxazolidinones and five-membered cyclic carbonates revealed that the cycloaddition reaction takes place through an asynchronous concerted mechanism in gas phase and in DCM.

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